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Due to their broken symmetry, chiral plasmonic nanostructures have unique optical properties and numerous applications. However, there is still a lack of comprehension regarding how chirality transfer occurs between circularly polarized light (CPL) and these structures. Here, we thoroughly investigate the plasmon-assisted growth of chiral nanoparticles from achiral Au nanocubes (AuNCs) via CPL without the involvement of any chiral molecule stimulators. We identify the structural chirality of our synthesized chiral plasmonic nanostructures using circular differential scattering (CDS) spectroscopy, which is correlated with scanning electron microscopy imaging at both the single-particle and ensemble levels. Theoretical simulations, including hot-electron surface maps, reveal that the plasmon-induced chirality transfer is mediated by the asymmetric distribution of hot electrons on achiral AuNCs under CPL excitation. Furthermore, we shed light on how this plasmon-induced chirality transfer can also be utilized for chiral growth in bimetallic systems, such as Ag or Pd on AuNCs. The results presented here uncover fundamental aspects of chiral light-matter interaction and have implications for the future design and optimization of chiral sensors and chiral catalysis, among others.
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http://dx.doi.org/10.1002/anie.202319920 | DOI Listing |
Org Biomol Chem
September 2025
School of Chemistry & Environment; Yunnan Key Laboratory of Chiral Functional Substance Research and Application, Yunnan Minzu University, Yuehua Street, Kun-ming 650504, China.
The present study utilizes density functional theory (DFT) to systematically investigate the effect of a ligand on the mechanism of nickel-catalyzed asymmetric hydrogenation of cyclic -sulfonyl imines, employing alcohol protons as the hydrogen source. By comparing the free energies of three catalytic pathways involving various coordinated nickel complexes with different ligands, we identify that the enantio-determining step is the nickel-hydride transfer. Notably, the reaction pathway initiated by the Ni(0) species through oxidative addition of alcohol is determined to be the most favorable.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Zinc(II) bis(triazolyl)(pyridyl)amine (Zn(BTPA)) complexes on the end of α-amino-iso-butyric acid (Aib) foldamers are able to transfer chirality from bound anions to the helical foldamer body. Zn(BTPA) could be obtained by simple synthetic methodology that allowed a range of functional groups to be installed around the binding site, exemplified with a fluorophore, a macrocyclic bridge and Aib itself. Changing functional group did not prevent chiral ligands from controlling foldamer conformation, although differences in complexation kinetics and equilibria were observed.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
By the strategic integration of squaramide with amino acid derivatives, a type of modular H-bonding catalyst for the enantioselective hydrogen atom transfer (HAT) process was developed. With these disulfides, a photoinduced asymmetric anti-Markovnikov hydrophosphinylation was achieved, providing a series of chiral -hydroxyphosphine oxides with reasonable to high enantioselectivity. Mechanism studies revealed the critical role of the H-bonding interactions between the squaramide scaffold and radical intermediates in governing the enantioselectivity and catalytic reactivity.
View Article and Find Full Text PDFChemistry
September 2025
ICGM, Univ, Montpellier, ENSCM, CNRS, Montpellier, France.
A novel Ru-catalyzed asymmetric transfer hydrogenation (ATH) strategy has been developed for the efficient synthesis of valuable chiral α-aminophosphonates from readily available α-iminophosphonates. This method enables the conversion of both acyclic and cyclic substrates in high yields (up to 97%) and excellent enantioselectivities (up to >99:1), providing a practical entry to phosphorus-containing chiral amines. Notably, this is the first reported application of ATH to α-iminophosphonates, offering a robust and operationally convenient alternative to conventional asymmetric hydrogenation (AH) approaches.
View Article and Find Full Text PDFOrg Lett
September 2025
Key Lab of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Wushan Rd-381, Guangzhou 510641, P.R. China.
Herein, we report the first regio- and enantioselective synthesis of tetrahydropyrido[2,3-]pyrazines using a chiral iridacycle catalyst. Pyridyl diamines and diketones undergo sequential annulation and asymmetric transfer hydrogenation of the generated pyrido[2,3-]pyrazine intermediates. This method provides diverse fused N-heterocycles in high yields (up to 95%) and enantioselectivity (98.
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